Reactivation of spent catalysts



C. L. THOMAS REACTIVATION OF SPENT CATALYST Jan. 11, 1944.

Filed Nov. l2, 1940 @Mib WSVNAN Patented Jan. 11, 1944- nach? UNITED STATES PATENT OFFICE REACTIVATION F SPENT CATALYSTS Charles L. Thomas, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Application November 12,1940, Serial No. 365,222 1 claim. (cl. 252-242) This invention relates to the reactivationof catalysts used in the conversion of petroleum hydrocarbons. More specifically it is concerned with a process for reactivatng catalystsl used in the reforming of low octane 'gasoline or naphthas to increase the octane number thereof.

When reforming gasoline and/or naphtha fractions, relatively'large amounts of carbon, or rather carbonaceous materials, are deposited upon the catalyst, thereby lowering its activity and life and necessitating frequent removal -of said contaminating deposits in order to restore the activity of the catalyst. In certain reforming operations it has been found desirable to mix hydrogen-containing gases with the charging stock in order to hydrogenate these carbonaceous deposits as they are being formed and thus increasing the length of the conversion portion of the operating cycle. Although the admixture of hydrogen with the charging stock reduces the amount of carbonaceous material deposited on the catalyst, under normal conditions of reforming operaitons the contamination of the catalyst is not entirely prevented and the use of the cating the partially reactivated catalyst to the acfil tion of an oxygen-containing gas under conditions suitable for the oxidation of `the remaining carbonaceous deposits and restoring the activity of the catalyst.

While my invention is not to be regarded as limited to any particular type of catalyst, it comprises the use of such catalysts as those prepared by compositing a relatively minor proportion of an oxide of an element selected from the membersv of the left-hand columns of groups IV, V and-VI of the periodic table with a relatively larger proportion of a refractory carrier, such as alumina, magnesia and silica. Thoria is another suitable carrier which may be composited -with an oxide selected from the left-hand columns of groups V and VI. A convenient method of preparing the composite catalyst consists in impregnating the major and less active constituent with a solution of some soluble salt of the more active constituent, as for example, the nitrates, evaporating the mixture to dryness fcllowed by ignition at a controlled temperature. An

alternate method of preparation, though sometimes less preferable, consists in mechanically alyst is intermittent, that is, a conversion period mixing carrier particles with the more active conis followed by a regeneration period. stituent, the latter being either in the Wet or dry It `has already been proposed to reactivate condition. i catalysts contaminated by hydrocarbon conver-A In the reforming process referred to in my insions by a hydrogenation process, but I have vention, the gasoline or naphtha fraction is subfound by experiment that such a treatment does jected to a catalyst of the above mentioned type not completely rejuvenate catalysts used in the at a temperature within the approximate range reforming operations with which my invention of *Z50-120W F. under a pressure which may vary is concerned. One of the disadvantages inherent from substantially atmospheric to as much as in the use of oxygen for reactivating spent cat- 1000 pounds 'per square inch, although at these alyst is the liberation of rather large quantities higher pressures less satisfactoryresults are obof heat which may raise the temperature of the tained than at pressures, as for example 15-300 catalyst to such a point so as to seriously dampounds per square inch. age it. The removal of the heat liberated in this As hereinbefore set forth, the charging stock way complicates design problems arising in the may be processed either alone or after admixconstruction of the reactors. I n the process com.- 40 ture with hydrogen-containing gases. The use prising 'my invention a considerable portion of of hydrogen-containing gases during the process the carbonaceous deposits is removed by hydro period will usually be found advisable as they genation, which step results in the liberation of result in a very considerable reduction in the smaller quantities of heat with a smaller risk carbonaceous deposits formed during the processof damaging the catalyst and with less trouble ing period and with consequent lengthening of removing the heat. the processing portion of the cycle. The use of In one specific embodiment my invention comhydrogen during the processing step also has the prises a process for reactivating a catalyst used advantage of producing a product of a low broin increasing the octane number of a motor fuel mine number and consequently greater susceptfraction comprising the steps of subjecting said 60 ibility to increase in octane number by addition used catalyst to the action of hydrogen-containof tetra-ethyl lead. The proportion of hydrogening gas under conditions suitable for the hydrocontaining gases to charging stock usually li'es genation of substantial portions of the contamiwithin the approximate limits of 0.5-15 mols nated carbonaceous deposits followed by subjectof hydrogen per mol of charging stock. 'I'he space velocities used in the conversion step are usually-*within the approximate limits of 0.2-40 volumes of liquid charging stools per hour per unit volume of catalyst. The optimum space velocity is a function of temperature, pressure and charging stock, but the values used usually lie within the range stated.

Fig. 1 in the accompanying drawing illustrates diagrammatically one specific form of apparatus in which the process of my invention may be conducted. le. y ,l

Charging. 'stock` for the process :which may comprise gasoline or naphtha is supplied to the system by way of line l controlled by valve 2 from which. it enters pump 3, discharging intoline It controlled by valve 5. After passing vtlirougli valve 5, the charging` stock enters line G wherein it is commingled with a hydrogen-containing gas and the mixture directed to heating coil il which is so disposed as to receive heat from. furnace 9. The heated products are discharged from coil at a temperature vwithin the approximate limits of 'TSG-i200o E. by way of line lil and after passaosassi of line l5 from which they pass throughvvalve V- to enter line i6, valve V- 4 being in the position ilustrated in Fig. 3. After passing through valve ll the hydrocarbon reactants are preferably quenched by well known means not shown in the drawing by hydrocarbon cooling oil, as forv example, heavy products formed in the process itself, and enter fractionating column I8 wherein the gasoline and lighter products are fractionated from 'the higher boiling material. The higher boiling products separated in fractionator lil are removed by way of line i9 controlled by valve 25 and collected as a product of ing through valve l@ pass through a four-walr valve V-B which is inthe position shown byFig. 2. After passing through valve l-3, the reactants enter reactor l2 wherein they are subjected to contact with a catalyst of the type hereinbefore set forth. In the particular :dow diagram illustrated in the drawing, two reactors operating in parallel are employed. Each reactor may i contain a plurality of tubes containing the catalytic material. These reactors may be equipped with means for introducing a fluid heating or cooling medium around the tubes for the purpose of supplying heat to, or removing heat from, the reaction zone. It is not intended that the invention should be limited in this respect as adiabatic reactors may be used. In such cases the catalyst is supported on a bed or aseries of beds or trays in an insulated chamber. In the adiabatic process the heat absorbed in the conversion process and the heat liberated in the regeneration step are taken from the hydrocarbon reactants or given up to the regenerating gases, respectively. When employing two reactors, one is at all times used as a reacting zone while the catalyst in the other is being reactivated as hereinafter set forth. The reactors are alternately operated with respect to the service for which they are ernployed by means of valves V--l and V-3 through which reactants and reactivating gases are supplied and withdrawn.

Any suitable valve arrangement capable of switching the reacting flow of the steam of reactants and the stream of regenerating gases may be employed within the scope of the invention and for the sake of simplifying the description and illustrating the process without unnecessary complications, the two switching valves V-3 and V--4 are herein illustrated as single four-Way valves in which the position of the two passageways therethrough may be shifted as illustrated in Figs. 2 and 3. Assuming that the valve V-3 tional ways.

the process. The gasoline and lower boiling products are removed from fractionating column I8 by way of line 2l land are directed to cooler and condenser 22. The mixture of liquid and vapors leaving cooling coil 22 enters line 23 and after passing through valve 2d enters receiver and separator 25. A. portion of the liquid product collected in receiver 25 enters pump 2l' by way of line 2b and is discharged into line 28 controlled by valve 29 and is supplied to fractionating column It for cooling and reux. The remainder of the liquid collected in receiver I8 enters pump 3l by way of line 30- and is discharged into line 32 controlled by valve 33 and is supplied to stabilizing column 34. Stabilizing column 34 operates in the conventional manner and is used to produce a motor fuel of the proper volatility, the stabilized product being removed rorn column 34 by way'of line 35 controlled by valve 36. The overhead product from stabilizer 34 is removed by way of line 31 and directed to cooler and condenser 38 from which the mixture oi condensed liquid and uncondensed and undissolved vapors enters line 39 which discharges into receiver and separator 40. The liquid separating in receiver 40 is removed by way of line @il and enters pump 42 which discharges into line 43 controlled by valve 44 from which it is returned to stabilizer 34 for cooling and re- The gases separated in receiver 25 are removed by Way of line 45 and after passing through valve 45 enter compressor 41 which discharges into line 48 and after passing through valve 49 are commingled with the gases obtained from receiver 40. The stabilizer gases obtained from receiver 40 are removed by way of line 50 and after passing through valve 5| enter compressor 52 which discharges into line 48 wherein said stabilizer gases are commingled with the gases obtained from receiver 25 as hereinbefore set forth. This mixture of gases then passes through valve 53 and enters absorber 54 wherein the greater portion of the hydrocarbon constituents thereof are dissolved in an absorbing oil. The rich absorption oil is removed from the bottom of the absorber 5ft by way of line 55 and after passing through pump 564 is discharged into line 5l controlled by valve 58. Line 5l discharges into stripping column 59 wherein the light hydrocarbon constituents are dissolved from the heavier absorption oil. The lean absorption oil leaves stripper 59 by way of line E0 and enters pump 6| discharging into line 62 controlled by valve 63 from which it is returned to absorber 54 for reuse. The light hydrocarbon gases stripped from the absorption oil are removed from stripper 59 by way of line 64 controlled by valve 65. Stripper 59 may be operated in a number of conven- If desired, steam may be used to Y 2,338,881 aid inremoving the iight dissolved constituents from the heavier oil.

The gases leaving absorber l by way of line 66 consists principally of hydrogen, together with smaller quantities of light gaseous hydrocarbons. These hydrogen-containing gases are dlrectdin part to line 61 and after passing through valve 68l enter compressor 69, discharging into line 6 hydrogenA to line 8|, the position of valve V-2 is so changed as to permit the passage oi' an inert purging gas introduced to the system by way of lline 83 controlled by valve 84 through valve V-2 to line 'I6 from which is passes through valve V--J into line 1] and thence to reactor I3'. After sev- I era1 minutes purging by the inert gas, air is in- Wheren they are commingled with the charging v between the approximate limits of 50G-1200" F..

and at a pressure which may vary from approximately 50 to about 2000 pounds per square inch and enter line 'I4 from which they are directed through three-Way valve V-I. The heated hydrogen-containing gases are used for partial reactivation of the catalyst as herelnbefore set forth. With valve V-I in the position as shown inthe drawing, these heated l'iydrogen-cont'ain-l ing gases enter line after which they pass through three-way valve V-2 to enter line 16.

From line 16 these heated hydrogen-containinggases pass through valve V-3 whichi is in the position shown by Fig. 2. After passing through valve V-3 they enter line 11 from which they are supplied to reactor I3 wherein they come in contact with the contaminated catalyst. As here;

inbefore set forth the hydrogen hydrogenates the' carbonaceous deposits forming volatile hydrocarbons, the mixture of hydrogen and hydrocarbons leaving reactor I3 byway of linev 'Il and passes through four-way valve V-l which is in the position shown in Fig. 3. This mixture of -hydrogen and light gaseous hydrocarbons is then directed to line 19 controlled by valve 80 from which it may be removed from the process 'and used for fuel. Ii desired, this mixture of hydrogen and hydrogen-containing gases obtained from reactor I3 might be directed to absorber 54 for removalof the greater portion of the hydrocarbons and for recycling `the hydrogen to the regenerating or conversion steps.

After the greater portion of the carbonaceous material has been removed bythe hydrogemthe position of the. valve V-l is so changed that the hydrogen is cut ofi from line 15 and directedto line 8l controlled by valve d2 and removed from the system. The hydrogen removed during this portion of the cycle may be used-.as a fuelif Aso desired 0r may be returned to the system for reuse in the process. After the position'of valve V-i has been so changed as to direct the heated troduced through line 83 and follows the same course as that just described for purging gas.

The air, which has been previously heated to a temperature of at least 750 F., is used to oxidize the remaining portion of the carbonaceous deposits on the surface of the lcatalyst.

The following example shows the type of results obtainable by the use of the process comprising my invention.

A Mid-Continent naphtha, of 52.5 A. P. I. gravity, 33.5 octane number by the C. F. R. motor method was passed over `a catalyst consisting of 92% alumina and 8% chromium oxide at a te'nperature of approximately 1000 F. for a period of 6 hours. A ratio of 4 mois of hydrogen to one mol of the charging stock was used, the mixture being under a pressure of 15 pounds per square inch gauge. During this period, a yield 'ofV 76.3 volume per centfgasoline having an octane number of 79.0 by the C. F. R. motor method was obtained. The catalyst at this time was contaminated with carbon to the extent of 2.06% by weight. passing a stream of light gases consisting of 85% hydrogen, the remainder consisting of liht gaseous hydrocarbons, principally methane, at a pressure of 1000 pounds per square inch and a temperature of 950 F. for a period of 30.fminutes. A sample of the catalyst was taken at this time and found to contain 0.45% carbonaceous material. A combustion gas substantially oxygen-free was then passed through the catalyst for a period of 3 minutes in order to purge the system ofhydrogen; A combustion gas containing 8 mol per cent of xygen heated to a temperature of 1000 F. was then passed over the catalyst for a, period .of 15 minutes after which time asample was taken of the catalyst and an analysis showed it' to contain 0.07% carbon.

I claim as my invention: In the reactivation of carbonized catalysts I which are damaged by excessive combustion temperatures, the method oi' lowering the amount of heat generated during thereactivation which comprises subjecting the catalyst to hydrogenation until a major portion of the carbonaceous deposits hasl been hydrosenated and removed from the catalyst, and subjecting /the thus par- ,tially reactivated catalyst to oxidation to burn an additional portion of the cerbonaceous de-Y posits therefrom. Y. y

CHARLES L. THOMAS.

The catalyst was them reactivated by 

